Copper Foil with Carrier, Method of Producing Same, Copper Foil with Carrier for Printed Wiring Board, and Printed Wiring Board

ABSTRACT

Provided is a copper foil for a printed wiring board including a roughened layer on at least one surface thereof. In the roughened layer, the average diameter D1 at the particle bottom being apart from the bottom of each particle by 10% of the particle length is 0.2 to 1.0 μm, and the ratio L1/D1 of the particle length L1 to the average diameter D1 at the particle bottom is 15 or less. In the copper foil for printed wiring board, when a copper foil for printed wiring having a roughened layer is laminated to a resin and then the copper layer is removed by etching, the sum of areas of holes accounting for the resin roughened surface having unevenness is 20% or more. The present invention involves the development of a copper foil for a semiconductor package substrate that can avoid circuit erosion without causing deterioration in other properties of the copper foil. In particular, an object of the present invention is to provide a copper foil for a printed wiring board and a method of producing the copper foil, in which the adhesion strength between the copper foil and the resin can be enhanced by improvement of the roughened layer of the copper foil.

TECHNICAL FIELD

The present invention relates to a copper foil with a carrier, a methodof producing the copper foil with a carrier, a copper foil with acarrier for a printed wiring board, and a printed circuit board. Morespecifically, the present invention relates to a copper foil with acarrier to be used as a material for printed wiring boards or shieldingmaterials.

BACKGROUND ART

A printed wiring board is generally produced by attaching an insulatingsubstrate to a copper foil to form a copper clad laminate and thenforming a conductor pattern on the copper foil surface by etching.Component mounting density and signal frequency have been increased,with the reduction in size and increase in need of high performance ofrecent electronic devices, and printed wiring boards have been requiredto have highly fine (fine pitch) conductor patterns and to cope withhigh frequencies.

Recently, the copper foil having a thickness of 9 μm or less, even 5 μmor less is demanded in accordance with fine pitches. Such an ultra-thincopper foil has low mechanical strength to readily cause tear orwrinkles during production of printed circuit boards. Thus, a copperfoil with a carrier composed of a thick metal foil as a carrier and anultra-thin copper layer electrodeposited onto the metal foil with arelease layer therebetween has been developed. The copper foil with acarrier is usually used by bonding the surface of the ultra-thin copperlayer to an insulating substrate by thermocompression bonding and thenpeeling the carrier with the release layer.

The surface of the ultra-thin copper layer of the copper foil with acarrier, i.e., the surface to be bonded to a resin, is primarilyrequired to have a sufficient peel strength between the ultra-thincopper layer and the resin base material and to sufficiently maintainthe peel strength after heating to high temperature, wet processing,soldering, chemical treatment, and other treatments.

In general, the peel strength between an ultra-thin copper layer and aresin base material is typically enhanced by allowing a large amount ofroughening particles to adhere to the ultra-thin copper layer toincrease the profile such as unevenness and roughness of the surface.

However, if such an ultra-thin copper layer having such an increasedprofile such as unevenness and roughness is applied to a semiconductorpackage substrate, which is a printed wiring board being particularlyrequired to have a fine circuit pattern, unnecessary copper particlesremain during circuit etching to cause defects such as insulationfailure between circuit patterns.

Accordingly, a copper foil with a carrier prepared without performingroughening treatment of the ultra-thin copper layer surface has beenused as the copper foil with a carrier for fine circuits such as asemiconductor package substrate. The adhesion (peel strength) to a resinof such an ultra-thin copper layer not subjected to roughening treatmentis apt to decrease compared to a copper foil for a general printedwiring board due to the low profile such as unevenness, degree ofroughness and roughness (see Patent Literature 8). Thus, the copper foilwith a carrier needs further improvement.

The copper foil for a semiconductor package substrate is also generallyreferred to as a copper foil for a printed wiring board and is usuallyproduced by the following procedure. First, a copper foil is laminatedand bonded to a base material such as a synthetic resin underhigh-temperature and high-pressure. Next, in order to form an intendedelectrically conductive circuit on a substrate, a circuit correspondingto the intended circuit is printed on the copper foil with a materialsuch as an etching resistant resin.

The unnecessary portion of the exposed copper foil is then removed byetching. After the etching, the printed portion of the materials such asthe resin is removed to form an electrically conductive circuit on thesubstrate. The formed electrically conductive circuit is finally formedinto a variety of printed circuit boards for electronic devices bysoldering specified elements.

Finally, the resulting circuit board is joined to a resist or build-upresin substrate. In general, the quality requirements for a copper foilfor a printed wiring board differ between the bonding surface (i.e.,roughened surface) to be bonded to a resin base material and thenon-bonding surface (i.e., glossy surface). Such different requirementshave to be simultaneously satisfied.

The requirements for the glossy surface include (1) satisfactoryappearance and no oxidative discoloration during storage, (2)satisfactory solder wettability, (3) no oxidative discoloration duringhigh-temperature heating, and (4) satisfactory adhesion with a resist.

On the other hand, the requirements for the roughened surface mainlyinclude (1) no oxidative discoloration during storage, (2) maintenanceof sufficient peel strength with a base material after high-temperatureheating, wet processing, soldering, chemical treatment, and othertreatment, and (3) no laminate spots after laminating with a basematerial or etching.

In addition, recent finer patterns demand lower profiles of a copperfoil; namely, an increase in peel strength of the roughened surface of acopper foil is necessary in accordance with it.

Furthermore, in electronic devices such as personal computers and mobilecommunication devices, as the speed and capacity of communicationincrease, the frequencies of electrical signals are increased. A printedwiring board and a copper foil that can cope with such progress aredemanded. An electrical signal frequency of 1 GHz or more significantlyincreases the influence of a skin effect, the current flowing only onthe surface of a conductor, to cause a change in current transmittingpath due to the unevenness of the surface and to thereby increase theimpedance to a level that is not negligible. From this point, thesurface roughness of a copper foil is desired to be small.

In order to satisfy such a requirement, a variety of methods of treatinga copper foil for a printed wiring board have been proposed.

In usual treatment of a copper foil for a printed wiring board, a rolledcopper foil or an electrolyzed copper foil is used, and rougheningtreatment, in general, application of microparticles made of copper orcopper oxide to the surface of the copper foil, is performed forincreasing the adhesiveness (peel strength) between the copper foil anda resin. Then, in order to give properties of heat-resistant/rustproof,a heat-resistant layer, in another word, ‘a barrier layer’ of brass orzinc is formed.

In order to avoid surface oxidation or the like during transportation orstorage, rust prevention treatment such as immersion or electrolyticchromate treatment or electrolytic chromium/zinc treatment is performedto yield a product.

Among these treatment processes, a roughened layer particularly has animportant part in enhancement of the adhesiveness (peel strength)between a copper foil and a resin. Conventionally, roundish or sphericalprojections have been believed to be suitable for the rougheningtreatment. Such roundish projections are obtained by suppressing thedevelopment of dendrites. However, the roundish projections are detachedat the time of etching, causing a phenomenon called “powder fall.” Sincethe contact area between the spherical projection and a copper foil isvery small compared to the diameter of the roundish or sphericalprojection, the phenomenon inevitably occurs.

In order to avoid this “powder fall” phenomenon, a thin copper platinglayer is formed on the projections after the roughening treatment toprevent the projections from peeling (see Patent Literature 1) off. Thishas an effect of preventing “powder fall”, but has disadvantages, thatis, an increase in the number of steps and a variation in the effect ofpreventing “powder fall” depending on the thin copper plating.

It is also reported on a technology of forming an acicular nodularcoating layer of an alloy of copper and nickel on a copper foil (PatentLiterature 2). This nodular coating layer has projections in an acicularform and is thereby believed to show higher adhesion strength with aresin compared to the roundish or spherical projections disclosed inPatent Literature 1. The layer is made of a copper-nickel alloy, whichis different from the component of the copper foil serving as the base,and is therefore etched at an etching rate different from that offorming a copper circuit. Consequently, such a layer is unsuitable for astable circuit design.

In formation of a copper foil for a printed wiring board, aheat-resistant/rustproof layer is usually formed. As examples of theheat-resistant treatment layer of a metal or alloy, coating layers ofZn, Cu—Ni, Cu—Co, or Cu—Zn are applied to a large number of copper foillayers in practical use (e.g., see Patent Literature 3).

In particular, a copper foil provided with a heat-resistant treatmentlayer made of Cu—Zn (brass) has excellent characteristics such thatlamination to a printed circuit board of, for example, an epoxy resindoes not cause spots of the resin layer and that the peel strength ishardly decreased by high-temperature heating and is therefore widelyused industrially.

Methods of forming the heat-resistant layer from brass are described indetail in Patent Literatures 4 and 5.

It has been proposed to improve the hydrochloric acid resistance bysubjecting the surface of a copper foil to roughening treatment, rustprevention treatment with zinc or a zinc alloy, and chromate treatmentand then adsorbing a silane coupling agent containing a small amount ofchromium ions to the chromate-treated surface (see Patent Literature 7).

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent Laid-Open No. H08-236930-   Patent Literature 2: Japanese Patent No. 3459964-   Patent Literature 3: Japanese Patent Publication No. S51-35711-   Patent Literature 4: Japanese Patent Publication No. S54-6701-   Patent Literature 5: Japanese Patent No. 3306404-   Patent Literature 6: Japanese Patent Application No. 2002-170827-   Patent Literature 7: Japanese Patent Laid-Open No. H03-122298-   Patent Literature 8: International Publication No. WO2004/005588

SUMMARY OF INVENTION Technical Problem

The present invention relates to a copper foil with a carrier for aprinted wiring board having excellent chemical resistance and adhesiveproperties, a method of producing the copper foil, a resin substrate forprinted wiring boards, and a printed wiring board. In particular, thepresent invention provides a copper foil with a carrier that can providehigh peel strength to a substrate for package, such as a bismaleimidetriazine (BT) resin-impregnated base material, in chemical treatmentduring fine pattern formation to allow fine etching and provides amethod of producing the copper foil and a printed wiring board.

Above all, an object of the present invention is to provide a copperfoil with a carrier for a printed wiring board, a method of producingthe copper foil, a resin substrate for a printed wiring board, and aprinted wiring board, wherein the adhesion strength between the copperfoil and the resin can be enhanced by improving the roughening treatmentto the layer of the copper foil and the steps.

Solution to Problem

The present inventors have diligently studied to solve theabove-described problems and as a result, provide the following copperfoil with a carrier for a printed wiring board, a method of producingthe copper foil, and a printed wiring board:

1) A Copper foil with a carrier comprising a carrier, an intermediatelayer, and an ultra-thin copper layer laminated in this order, whereinthe ultra-thin copper layer includes a roughened layer on a surfacethereof, and the roughened layer comprises particles having an averagediameter D1 of 0.2 to 1.0 μm at the particle bottom being apart from thebottom of each particle by 10% of the particle length L1 and having aratio L1/D1 of the particle length L1 to the average diameter D1 at theparticle bottom of 15 or less;

2) The copper foil with a carrier according to 1) above, wherein on asurface of the ultra-thin copper layer, the ratio D2/D1 of the averagediameter D2 at the particle middle being apart from the bottom of eachparticle by 50% of the particle length to the average diameter D1 at theparticle bottom is 1 to 4;

3) The copper foil with a carrier according to 2) above, wherein theratio D2/D3 of the average diameter D2 at the particle middle to theaverage diameter D3 at the particle end being apart from the bottom ofeach particle by 90% of the particle length is 0.8 to 1.0;

4) The copper foil with a carrier according to 2) or 3) above, whereinthe average diameter D2 at the particle middle is 0.7 to 1.5 μm;

5) The copper foil with a carrier according to 3) or 4) above, whereinthe average diameter D3 at the particle end is 0.7 to 1.5 μm;

6) The copper foil with a carrier according to any one of 1) to 5)above, further comprising a heat-resistant/rustproof layer containing atleast one element selected from zinc, nickel, copper, phosphorus, andcobalt on the roughened layer, a chromate film layer on theheat-resistant/rustproof layer, and a silane coupling agent layer on thechromate film layer;

7) A method of producing a copper foil with a carrier according to anyone of 1) to 6) above, the method comprising forming a roughened layerusing a sulfuric acid/copper sulfate electrolytic bath containing atleast one material selected from alkyl sulfates, tungsten, and arsenic;

8) The method of producing a copper foil with a carrier according to 7)above, further comprising forming a heat-resistant/rustproof layercontaining at least one element selected from zinc, nickel, copper,phosphorus, and cobalt on the roughened layer, forming a chromate filmlayer on the heat-resistant/rustproof layer, and forming a silanecoupling agent layer on the chromate film layer;

9) A copper foil with a carrier for a printed wiring board comprising acarrier, an intermediate layer, and an ultra-thin copper layer laminatedin this order, wherein the ultra-thin copper layer includes a roughenedlayer on a surface thereof; and when the copper foil with a carrier islaminated to a resin layer, then the carrier and the intermediate layerare peeled from the ultra-thin copper layer, and then the ultra-thincopper layer is removed by etching, the sum of areas of holes accountingfor the roughened surface of the resin layer having unevenness is 20% ormore of the resin surface;

10) The copper foil with a carrier for a printed wiring board, whereinwhen the copper foil with corrier according to any one of 1) to 8) abovecomprising the roughened layer is laminated to a resin, then the carrierand the intermediate layer are peeled from the ultra-thin copper layer,and then the ultra-thin copper layer is removed by etching, the sum ofareas of holes accounting for the roughened surface of the resin layerhaving unevenness transferred from the roughened surface of theultra-thin copper layer is 20% or more of the resin surface;

11) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier including a carrier, an intermediate layer,and an ultra-thin copper layer laminated in this order and including aroughened layer on a surface of the ultra-thin copper layer, peeling thecarrier and the intermediate layer from the ultra-thin copper layer,removing the ultra-thin copper layer by etching, plating the exposedresin surface by electroless copper plating and electroplating in thisorder to form a copper layer, and forming a circuit by etching;

12) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier including a roughened layer according to anyone of 1) to 8) above, peeling the carrier and the intermediate layerfrom the ultra-thin copper layer, removing the ultra-thin copper layerby etching, plating the exposed resin surface by electroless copperplating and electroplating in this order to form a copper layer, andforming a circuit by etching;

13) A printed wiring board formed by laminating a resin layer to thecopper foil with a carrier according to any one of 1) to 10) above,peeling the carrier and the intermediate layer from the ultra-thincopper layer, removing the ultra-thin copper layer by etching, andforming a circuit on the exposed resin surface;

14) A printed wiring board formed by laminating a resin layer to thecopper foil with a carrier according to any one of 1) to 10) above,peeling the carrier and the intermediate layer from the ultra-thincopper layer, removing the ultra-thin copper layer by etching, forming acopper layer on the exposed resin surface, and forming a circuit;

15) The printed wiring board according to any one of 11) to 14) above,wherein five or more acicular particles are formed within a circuitwidth of 10 μm;

16) The copper foil with a carrier according to 14) or 15) above,wherein the resin layer is composed of an adhesive resin;

17) The copper foil with a carrier according to any one of 14) to 16)above, wherein the resin layer is composed of a resin in a semi-curedstate;

18) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier including a carrier, an intermediate layer,and an ultra-thin copper layer laminated in this order and including aroughened layer on a surface of the ultra-thin copper layer, peeling thecarrier and the intermediate layer from the ultra-thin copper layer,removing the ultra-thin copper layer by etching, plating the exposedresins surface by electroless copper plating and electroplating in thisorder to form a copper layer, and forming a circuit by etching;

19) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier according to any one of 1) to 9) and 12) to17) above, peeling the carrier and the intermediate layer from theultra-thin copper layer, removing the ultra-thin copper layer byetching, plating the exposed resin surface by electroless copper platingand electroplating in this order to form a copper layer, and forming acircuit by etching;

20) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier according to any one of 1) to 9) and 12) to17) above, peeling the carrier and the intermediate layer from theultra-thin copper layer, removing the ultra-thin copper layer byetching, and forming a circuit on the exposed resin surface;

21) A printed wiring board formed by laminating a resin layer to acopper foil with a carrier according to any one of 1) to 9) and 12) to17) above, peeling the carrier and the intermediate layer from theultra-thin copper layer, removing the ultra-thin copper layer byetching, forming a copper layer on the exposed resin surface, andforming a circuit;

22) A printed wiring board produced using the copper foil with a carrieraccording to any one of 1) to 9) and 12) to 17) above;

23) A printed circuit board produced using the copper foil with acarrier according to any one of 1) to 9) and 12) to 17) above;

24) A copper clad laminate produced using the copper foil with a carrieraccording to any one of 1) to 9) and 12) to 17) above;

25) The printed wiring board according to any one of 18) to 22) above,wherein five or more acicular particles are formed within a circuitwidth of 10 μm;

26) The printed circuit board according to 23) above, wherein five ormore acicular particles are formed within a circuit width of 10 μm; and

27) A method of producing a printed wiring board, the method comprisingthe steps of preparing the copper foil with a carrier according to anyone of 1) to 9) and 12) to 17) above and an insulating substrate,laminating the copper foil with a carrier and the insulating substrate,peeling the copper foil carrier of the copper foil with a carrier fromthe laminate comprising the copper foil with a carrier and theinsulating substrate to form a copper clad laminate, and forming acircuit by any process selected from a semi-additive process, asubtractive process, a partially additive process, or a modifiedsemi-additive process.

Effects of Invention

As described above, the copper foil with a carrier for a printed wiringboard of the present invention includes acicular or rod-like fineroughening particles on at least one surface of the copper foil, insteadof the roundish or spherical projections that have been conventionallybelieved to be good for roughening treatment.

The copper foil has an excellent effect of increasing the adhesionstrength with resin to provide high peel strength to a substrate forpackage in chemical treatment during fine-pattern formation and therebyallowing fine etching of a printed wiring board. The copper foil with acarrier is also useful for a method of increasing adhesion strength witha copper plating layer for a circuit (electroless plating layer)subsequently formed on a surface of a resin by once removing a copperlayer completely to transfer a roughened surface to the resin. In recentincreases in fineness of printed circuit patterns and in frequency, thecopper foil with a carrier for a printed circuit board of the presentinvention is significantly effective as a copper foil for a printedcircuit (copper foil for a semiconductor package substrate) or asubstrate for semiconductor package composed of a copper foil for asemiconductor package substrate and a resin for semiconductor packagebonded to each other.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram schematically illustrating a particle size.

FIG. 2 shows an FIB-SIM photograph (the left) of the roughened layer ofExample 1 and an SEM photograph (the right) of a resin (replica) surfaceprepared by laminating a resin to a copper layer and then removing thecopper layer by etching.

FIG. 3 shows an FIB-SIM photograph of the roughened layer of ComparativeExample 1 and an SEM photograph (the right) of a resin (replica) surfaceprepared by laminating a resin to a copper layer and then removing thecopper layer by etching.

DETAILED DESCRIPTION

The present invention will now be described specifically and in detailfor facilitating understanding of the present invention. The copper foilused in the present invention may be an electrolyzed copper foil or arolled copper foil.

As described above, the copper foil with a carrier for a printed wiringboard of the present invention includes acicular or rod-like fineroughening copper particles on at least one surface of the copper foil,instead of the roundish or spherical projections that have beenconventionally believed to be good for roughening treatment.

The copper foil includes a roughened layer having a shape such that theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length is 0.2 to 1.0 μm and thatthe ratio L1/D1 of the particle length L1 to the average diameter D1 atthe particle bottom is 15 or less. More preferably, the roughened layeris provided on at least one surface of the copper foil and has a shapesuch that the ratio D2/D1 of the average diameter D2 at the particlemiddle being apart from the bottom of each particle by 50% of theparticle length to the average diameter D1 at the particle bottom is 1to 4.

Furthermore, the ratio D2/D3 of the average diameter D2 at the particlemiddle to the average diameter D3 at the particle end being apart fromthe bottom of each particle by 90% of the particle length can be 0.8 to1.0. In this case, the average diameter D2 at the particle middle ispreferably 0.7 to 1.5 μm, and the average diameter D3 at the particleend is preferably 0.7 to 1.5 μm.

FIG. 1 is a diagram schematically illustrating a particle size. FIG. 1shows the average diameter D1 at the particle bottom being apart fromthe bottom of each particle by 10% of the particle length, the averagediameter D2 at the particle middle being apart from the bottom of eachparticle by 50% of the particle length, and the average diameter D3 atthe particle end being apart from the bottom of each particle by 90% ofthe particle length. This specification can identify the particle shape.

Furthermore, a heat-resistant/rustproof layer containing at least oneelement selected from zinc, nickel, copper, phosphorus, and cobalt canbe formed on the roughened layer, a chromate film layer can be formed onthe heat-resistant/rustproof layer, and a silane coupling agent layercan be formed on the chromate film layer.

The roughened layer of such a copper foil can be formed using a sulfuricacid/copper sulfate electrolytic bath containing at least one materialselected from alkyl sulfates, tungsten, and arsenic, and the shapedescribed above can be achieved by appropriately setting electrolytictreatment conditions. Furthermore, a heat-resistant/rustproof layercontaining at least one element selected from zinc, nickel, copper,phosphorus, and cobalt can be formed on the roughened layer, a chromatefilm layer can be formed on the heat-resistant/rustproof layer, and asilane coupling agent layer can be formed on the chromate film layer.

The copper foil provided with the roughened layer can be formed into alaminate with a resin by a pressing or lamination process.

Upon removing the copper layer from the laminate composed of the copperfoil having a roughened layer and the resin by etching, the unevennessof the roughened surface of the copper foil is transferred to the resinafter the removal of the copper layer. The unevenness transferred to theresin corresponds to the shapes and number distribution of theroughening particles on the copper foil surface and is important. If theparticles of the rough surface of the copper foil have small diametersat the bottom positions, the transferred holes have small diameters, andthe sum of areas of the holes is small.

In the case of particles having small diameters at the bottom positions,i.e., particles in a reverse teardrop shape, of the rough surface of acopper foil, the adhesiveness between the copper foil and a resin isincorrectly thought to increase at first glance, but since the adheringwidth of the roughening particles with the copper layer is narrow, theroughening particles are apt to break at the bottom when the copperlayer is peeled from the resin layer. As a result, the copper layer ispeeled at the interface between the copper layer and the rougheningparticles or at the broken bottom portion of the roughening particlesresulting in decreased adherence. The sum of areas of the holes isrequired to account for 20% or more of the resin surface.

If the particles of the rough surface of the copper foil have smalldiameters at the bottom positions, the holes formed on the resin surfaceafter removing the copper layer by etching have small sizes.Consequently, even in electroless plating of the resin surface, theelectroless plating solution cannot enter the holes, resulting inincomplete electroless plating, which causes a problem of, a reductionin the peel strength of the plating.

Thus, the particles of roughened surface of a copper foil need to have acertain diameter and a certain length, and the sum of areas of the holesaccounting for the resin surface having unevenness transferred from therough surface of the copper foil is important. The peel strength of acircuit can be improved by increasing the sum to 20% or more.

As described above, a printed wiring board can be produced by laminatinga copper foil including a roughened layer to a resin layer, removing thecopper layer by etching, plating the exposed resin surface byelectroless copper plating and copper electroplating in this order toform a copper layer, and forming a circuit by etching. An electrolessplating/electroplating layer, i.e., a copper layer is formed on theunevenness of the rough surface of the resin substrate to form acicularor rod-like particles reflecting the unevenness of the resin surface.

It is preferable to form five or more acicular or rod-like particleswithin a circuit width of 10 μm. By doing so, the adhesion strengthbetween the resin and the circuit layer by electroless plating can benotably improved. The present invention provides a printed wiring boardproduced as in above.

As described above, the roughened layer composed of acicular or rod-likefine roughening particles of copper can be produced using a sulfuricacid/copper sulfate electrolytic bath containing at least one materialselected from alkyl sulfates, tungsten, and arsenic.

The roughened layer composed of acicular fine roughening particles ofcopper is preferably subjected to overlay plating in a sulfuricacid/copper sulfate electrolytic bath for preventing powder fall andimproving the peel strength.

Specific treatment conditions are as follows:

(Liquid Composition 1)

-   -   Cu: 10 to 30 g/L    -   H₂SO₄: 10 to 150 g/L    -   W: 0 to 50 mg/L    -   Sodium dodecyl sulfate: 0 to 50 mg    -   As: 0 to 2000 mg/L

(Electroplating Condition 1)

-   -   Temperature: 30 to 70° C.

(Electric Current Condition 1)

-   -   Current density: 25 to 110 A/dm²    -   Roughening coulomb quantity: 50 to 500 As/dm²    -   Plating time: 0.5 to 20 seconds

(Liquid Composition 2)

-   -   Cu: 20 to 80 g/L    -   H₂SO₄: 50 to 200 g/L

(Electroplating Condition 2)

-   -   Temperature: 30 to 70° C.

(Electric Current Condition 2)

-   -   Current density: 5 to 50 A/dm²    -   Roughening coulomb quantity: 50 to 300 As/dm²    -   Plating time: 1 to 60 seconds

Furthermore, a heat-resistant/rustproof layer containing at least oneelement selected from zinc, nickel, copper, phosphorus, and cobalt isformed on the roughened layer, a chromate film layer is formed on theheat-resistant/rustproof layer, and a silane coupling agent layer isformed on the chromate film layer to give a copper foil for a printedwiring board.

Any conventional heat-resistant/rustproof layer can be used as theheat-resistant/rustproof layer without particular limitation. Forexample, a brass coating layer, which has been conventionally used, canbe used in the copper foil for a semiconductor package substrate.

On the heat-resistant/rustproof layer, a chromate film layer and asilane coupling agent layer are formed, which are used as bondingsurfaces to at least the resin of a copper foil. The copper foil havinga coating layer composed of these chromate film layer and silanecoupling agent layer is laminated and bonded to a resin. An etchingresistant printed circuit is further formed on the copper foil, and thenunnecessary portion of the copper foil excluding the printed circuitportion is removed by etching to form an electrically conductivecircuit.

For a heat resistant and rust proof layer, existing treatments can beused. Specifically, the followings can be used as an example:

(Liquid Composition)

-   -   NaOH: 40 to 200 g/L    -   NaCN: 70 to 250 g/L    -   CuCN: 50 to 200 g/L    -   Zn(CN)₂: 2 to 100 g/L    -   As₂O₃: 0.01 to 1 g/L

(Liquid Temperature)

-   -   40 to 90° C.

(Electric Current Condition)

-   -   Current density: 1 to 50 A/dm²    -   Plating time: 1 to 20 seconds

As the chromate film layer, an electrolytic chromate film layer or animmersion chromate film layer can be used. Preferably, the chromate filmlayer contains 25 to 150 μg/dm² of Cr.

A Cr amount less than 25 μg/dm² does not show an effect as a rustprooflayer. In a Cr amount exceeding 150 μg/dm², the effect is saturated, andsuch an amount is therefore wasteful. Thus, preferably, the Cr amount is25 to 150 μg/dm².

Examples of the conditions for forming the chromate film layer are shownbelow. As described above, however, the conditions are not limitedthereto, and various known chromate treatment processes can be employed.This rust prevention treatment is one factor that affects acidresistance, and chromate treatment improves the acid resistance.

(a) Immersion Chromate Treatment

-   -   K₂Cr₂O₇: 1 to 5 g/L, pH: 2.5 to 4.5, temperature: 40 to 60° C.,        time: 0.5 to 8 seconds

(b) Electrolytic Chromate Treatment (Chromium/Zinc Treatment (AlkalineBath))

-   -   K₂Cr₂O₇: 0.2 to 20 g/L, acid: phosphoric acid, sulfuric acid,        organic acid, pH: 1.0 to 3.5, temperature: 20 to 40° C., current        density: 0.1 to 5 A/dm², time: 0.5 to 8 seconds

(c) Electrolytic Chromium/Zinc Treatment (Alkaline Bath)

-   -   K₂Cr₂O₇ (Na₂Cr₂O₇ or CrO₃): 2 to 10 g/L, NaOH or KOH: 10 to 50        g/L, ZnOH or ZnSO₄.7H₂O: 0.05 to 10 g/L, pH: 7 to 13,    -   bath temperature: 20 to 80° C., current density: 0.05 to 5        A/dm², time: 5 to 30 seconds

(d) Electrolytic Chromate Treatment (Chromium/Zinc Treatment (AcidicBath))

-   -   K₂Cr₂O₇: 2 to 10 g/L, Zn: 0 to 0.5 g/L, Na₂SO₄: 5 to 20 g/L,    -   pH: 3.5 to 5.0, bath temperature: 20 to 40° C.,    -   current density: 0.1 to 3.0 A/dm², time: 1 to 30 seconds

As the silane coupling agent layer used in the copper foil for asemiconductor package substrate of the present invention, a silanecoupling agent that is usually used in a copper foil can be used withoutparticular limitation. For example, specific conditions for silanetreatment are as follows.

An aqueous 0.2 vol % 3-glycidoxypropyltrimethoxysilane solution issprayed and then heating and drying is performed in an air of 100 to200° C. for 0.1 to 10 seconds.

A silane coupling agent containing a tetraalkoxysilane and at least onealkoxysilane having a functional group reactive to a resin can be used.Any silane coupling agent layer can also be used, but preferably, thesilane coupling agent is selected in the light of adhesive propertieswith resin.

(Carrier)

As the carrier of the copper foil with a carrier of the presentinvention, a foil such as a copper foil, an aluminum foil, an aluminumalloy foil, an iron alloy foil, a stainless steel foil, a nickel foil,or a nickel alloy foil can be used. Preferably, a copper foil is used inview of easiness in lamination of an intermediate layer onto a carrier.The copper foil used in the carrier is typically provided in a form ofrolled or electrolyzed. The electrolyzed copper foil is generallyproduced by electrolytically depositing copper onto a drum of titaniumor stainless steel from a copper sulfate plating bath. The rolled copperfoil is produced by plastic forming via rolling roll and heat treatmentrepeatedly.

Examples of usable materials for a copper foil include a high-puritycopper such as a tough pitch copper and an oxygen-free copper,Sn-containing copper alloys, Ag-containing copper alloys, Cr-, Zr-, orMg-added copper alloys, and copper alloys such as Corson based alloycontaining Ni and Si. Throughout the specification, the term “copperfoil” used alone includes copper alloy foil.

The carrier used in the present invention may have any thickness withoutparticular limitation. The thickness of the carrier may be appropriatelycontrolled so as to achieve the purpose, such as 12 μm or more. Since anexcessive thickness, however, increases the production cost, in general,the thickness is preferably 35 μm or less. Thus, the carrier preferablyhas a thickness of 12 to 70 μm and more preferably 18 to 35 μm.

(Intermediate Layer)

An intermediate layer is disposed on the carrier. The intermediate layerof the copper foil with a carrier of the present invention is preferablya layer containing at least one selected from the group consisting ofCr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, alloys, hydrates, and oxidesthereof, and organic compounds. The intermediate layer may be amultilayer.

For example, the intermediate layer is constituted of, from the carrierside, a monometal layer of one element selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al or an alloy layerof one or more elements selected from the group consisting of Cr, Ni,Co, Fe, Mo, Ti, W, P, Cu, and Al; and a layer of a hydrate or oxide ofone or more elements selected from the group consisting of Cr, Ni, Co,Fe, Mo, Ti, W, P, Cu, and Al.

Furthermore, the intermediate layer may be constituted of, for example,two layers of Ni and Cr. The Ni layer and the Cr layer are laminatedsuch that the Ni layer is in contact with the interface with the copperfoil carrier and that the Cr layer is in contact with the interface withthe ultra-thin copper layer. The deposition amount of Cr of theintermediate layer can be 10 to 100 μg/dm², and the deposition amount ofNi can be 1000 to 40000 μg/dm².

(Ultra-Thin Copper Layer)

An ultra-thin copper layer is disposed on the intermediate layer. Theultra-thin copper layer of the copper foil with a carrier of the presentinvention can be formed by electroplating using an electrolytic bath ofcopper sulfate, copper pyrophosphate, copper sulfamate, or coppercyanide and the like. Preferably, a copper sulfate bath, which isgenerally used in electrolyzed a copper foil and allows formation of acopper foil at a high current density, is used. The ultra-thin copperlayer may have any thickness without particular limitation and generallyhas a thickness smaller than that of the carrier, e.g., 12 μm or less.The thickness is preferably 0.1 to 12 μm, more preferably 0.5 to 12 μm,and most preferably 2 to 5 μm.

(Copper Foil with a Carrier)

Thus, an intermediate layer is laminated to a carrier, and a copper foilwith a carrier including an ultra-thin copper layer laminated to theintermediate layer is produced.

The copper foil with a carrier including a carrier, an intermediatelayer laminated to the carrier, and an ultra-thin copper layer laminatedto the intermediate layer may include a roughened layer on theultra-thin copper layer and may include at least one layer selected fromthe group consisting of heat-resistant/rustproof layers, chromate filmlayers, and silane coupling agent layers on the roughened layer.

The roughened layer may be disposed on the ultra-thin copper layer, aheat-resistant/rustproof layer may be disposed on the roughened layer, achromate film layer may be disposed on the heat-resistant/rustprooflayer, and a silane coupling agent layer may be disposed on the chromatefilm layer.

In the copper foil with a carrier, a resin layer may be disposed on theroughened layer, on the heat-resistant/rustproof layer, chromate filmlayer, or silane coupling agent layer. The resin layer may be aninsulating resin layer.

The resin layer may be an adhesive agent or may be an insulating resinlayer in a semi-cured state (B stage) for bonding. In the semi-curedstate (B stage state), no adhesive feeling is given when a fingertouches the surface of the layer, the insulating resin layers can bestored in a stacked state, and also a curing reaction is caused by heattreatment.

The resin layer may contain a thermosetting resin or may be athermoplastic resin. The resin layer may contain a thermoplastic resin.The type of the resin is not particularly limited, and preferredexamples of the resin include epoxy resins, polyimide resins,polyfunctional cyanic ester compounds, maleimide compounds, polyvinylacetal resins, and urethane resins.

Such a resin is dissolved in a solvent such as methyl ethyl ketone (MEK)or toluene to prepare a resin solution; the resin solution is appliedonto the ultra-thin copper layer or the heat-resistant/rustproof layer,chromate film layer, or silane coupling agent layer by roll coater, forexample; and then the solvent is removed by heat drying as necessary togive the B stage state. The drying may be performed, for example, usinga hot-air drying furnace at a drying temperature of 100 to 250° C.,preferably 130 to 200° C.

The copper foil with a carrier having the resin layer (a resin-providedcopper foil with a carrier) is used as follows: The resin layer islaminated to a base material and is thermally cured by thermocompressionbonding thereof; the carrier is peeled to expose the ultra-thin copperlayer (the surface of the ultra-thin copper layer on the intermediatelayer side); and a predetermined wiring pattern is formed on the exposedultra-thin copper layer surface.

The use of the resin-provided copper foil with a carrier can reduce thenumber of sheets of the prepreg material used in production of amultilayer printed circuit board. In addition, it is possible to controlthe thickness of the resin layer for securing interlayer insulation orto produce a copper clad laminate without using any prepreg material atall. On this occasion, it is also possible to further improve thesmoothness of the surface of the base material by undercoating thesurface with an insulating resin.

The case not using any prepreg material can save the material cost forthe prepreg material and simplify the lamination step, which iseconomically advantageous and also reduces the thickness of theresulting multilayer printed circuit board by an amount corresponding tothe thickness of the prepreg material. As a result, advantageously, anultra-thin multilayer printed circuit board, each layer of which has athickness of 100 μm or less, can be produced.

The thickness of the resin layer is preferably 0.1 to 80 μm.

A thickness of the resin layer of less than 0.1 μm gives a low adhesivestrength. Thus, if the resin-provided copper foil with a carrier islaminated to a base material including an inner layer material withoutinterposing a prepreg material therebetween, it may be difficult tosecure interlayer insulation between the resin layer and the circuit ofthe inner layer material.

In contrast, a resin layer having a thickness exceeding 80 μm isdifficult to be formed by application only once, which requires extramaterial cost and step and is therefore economically disadvantageous.And, the resulting resin layer is inferior in flexibility to readilycause, for example, cracks during handling or may cause excessive resinflow during thermocompression bonding with an inner layer material,resulting in difficulty in smooth lamination.

Furthermore, in another product form of the resin-provided copper foilwith a carrier, it is also possible to produce in a form of aresin-provided copper foil not having a carrier by forming a resin layerso as to coat the ultra-thin copper layer, the heat-resistant/rustprooflayer, chromate film layer, or silane coupling agent layer; semi-curingthe resin; and the peeling the carrier.

It is known to those skilled in the art how to use the copper foil witha carrier itself. For example, the surface of the ultra-thin copperlayer is bonded to an insulating substrate such as a paper base phenolicresin, a paper base epoxy resin, a synthetic fiber fabric base epoxyresin, a glass fabric/paper composite base epoxy resin, a glassfabric/nonwoven glass fabric composite base epoxy resin, a glass fabricbase epoxy resin, a polyester film, or a polyimide film. Afterthermocompression bonding, the carrier is peeled. The ultra-thin copperlayer bonded to the insulating substrate is etched into an intendedconductor pattern to finally produce a printed wiring board. Electronicparts are further mounted on the printed wiring board to give a printedcircuit board. Some examples of processes of producing a printed wiringboard including the copper foil with a carrier of the present inventionwill now be described.

In an embodiment of the method of producing the printed wiring board ofthe present invention, the method includes a step of preparing a copperfoil with a carrier of the present invention and an insulatingsubstrate, a step of laminating the copper foil with a carrier and theinsulating substrate such that the ultra-thin copper layer side of thecopper foil with a carrier faces the insulating substrate, a step ofpeeling the carrier of the copper foil with a carrier to form a copperclad laminate, and a step of forming a circuit by any of a semi-additiveprocess, a modified semi-additive process, a partially additive process,and a subtractive process. The insulating substrate may include aninnerlayer circuit.

The semi-additive process in the present invention refers to a method offorming thin plating on an insulating substrate or a copper foil seedlayer by electroless plating, forming a pattern, and forming a conductorpattern by electroplating and etching.

Accordingly, in an embodiment of the method of producing the printedwiring board of the present invention employing the semi-additiveprocess, the method includes a step of preparing a copper foil with acarrier of the present invention and an insulating substrate, a step oflaminating the copper foil with a carrier and the insulating substrate,a step of peeling the carrier of the copper foil with a carrier from thelaminate composed of the copper foil with a carrier and the insulatingsubstrate, a step of completely removing the ultra-thin copper layer,exposed by the peeling of the carrier, by a process such as etchingusing an etchant such as an acid or plasma etching, a step of providinga through-hole and/or a blind via in the resin exposed by the removal ofthe ultra-thin copper layer by etching, a step of subjecting the regioncontaining the through-hole and/or the blind via to desmear treatment, astep of providing an electroless plating layer to the resin and theregion containing the through-hole and/or the blind via, a step ofproviding a plating resist on the electroless plating layer, a step ofexposing the plating resist to light and then removing the platingresist in the region where a circuit is formed, a step of providing anelectroplating layer to the plating resist-removed region where thecircuit is formed, a step of removing the plating resist, and a step ofremoving the electroless plating layer in the region excluding theregion where the circuit is formed by, for example, flash etching.

In another embodiment of the method of producing the printed wiringboard of the present invention employing the semi-additive process, themethod includes a step of preparing a copper foil with a carrier of thepresent invention and an insulating substrate, a step of laminating thecopper foil with a carrier and the insulating substrate, a step ofpeeling the carrier of the copper foil with a carrier from the laminatecomposed of the copper foil with a carrier and the insulating substrate,a step of completely removing the ultra-thin copper layer, exposed bythe peeling of the carrier, by a process such as etching using anetchant such as an acid or plasma etching, a step of providing anelectroless plating layer on the surface of the resin exposed byremoving the ultra-thin copper layer by etching, a step of providing aplating resist on the electroless plating layer, a step of exposing theplating resist to light and then removing the plating resist in theregion where a circuit is formed, a step of providing an electroplatinglayer to the plating resist-removed region where the circuit is formed,a step of removing the plating resist, and a step of removing theelectroless plating layer and the ultra-thin copper layer in the regionexcluding the region where the circuit is formed by, for example, flashetching.

The modified semi-additive process in the present invention refers to amethod of forming a circuit on an insulating layer by laminating metalfoil to the insulating layer, protecting a region where the circuit isnot formed by a plating resist, thickening the copper in thecircuit-forming region by electroplating, removing the resist, andremoving the metal foil in the region excluding the circuit-formingregion by (flash) etching.

Accordingly, in an embodiment of the method of producing the printedwiring board of the present invention employing the modifiedsemi-additive process, the method includes a step of preparing a copperfoil with a carrier of the present invention and an insulatingsubstrate, a step of laminating the copper foil with a carrier and theinsulating substrate, a step of peeling the carrier of the copper foilwith a carrier from the laminate composed of the copper foil with acarrier and the insulating substrate, a step of providing a through-holeand/or a blind via in the ultra-thin copper layer and the insulatingsubstrate exposed by the peeling of the carrier, a step of subjectingthe region containing the through-hole and/or the blind via to desmeartreatment, a step of providing an electroless plating layer in theregion containing the through-hole and/or the blind via, a step ofproviding a plating resist on the surface of the ultra-thin copper layerexposed by peeling of the carrier, a step of forming a circuit byelectroplating after the provision of the plating resist, a step ofremoving the plating resist, and a step of removing the ultra-thincopper layer, exposed by the removal of the plating resist, by flashetching.

In another embodiment of the method of producing the printed wiringboard of the present invention employing the modified semi-additiveprocess, the method includes a step of preparing a copper foil with acarrier of the present invention and an insulating substrate, a step oflaminating the copper foil with a carrier and the insulating substrate,a step of peeling the carrier of the copper foil with a carrier from thelaminate composed of the copper foil with a carrier and the insulatingsubstrate, a step of providing a plating resist on the ultra-thin copperlayer exposed by the peeling of the carrier, a step of exposing theplating resist to light and then removing the plating resist in theregion where a circuit is formed, a step of providing an electroplatinglayer to the plating resist-removed region where the circuit is formed,a step of removing the plating resist, and a step of removing theelectroless plating layer and the ultra-thin copper layer in the regionexcluding the region where the circuit is formed by, for example, flashetching.

The partially additive process in the present invention refers to amethod of producing a printed wiring board by applying a catalyticnucleus onto a substrate provided with a conductor layer and optionallyprovided with a hole as a through-hole or via-hole, forming a conductorcircuit by etching, optionally providing a solder resist or a platingresist, and then performing electroless plating treatment on theconductor circuit, the through-hole or via-hole, for thickening.

Accordingly, in an embodiment of the method of producing the printedwiring board of the present invention employing the partially additiveprocess, the method includes a step of preparing a copper foil with acarrier of the present invention and an insulating substrate, a step oflaminating the copper foil with a carrier and the insulating substrate,a step of peeling the carrier of the copper foil with a carrier from thelaminate composed of the copper foil with a carrier and the insulatingsubstrate, a step of providing a through-hole and/or a blind via in theultra-thin copper layer and the insulating substrate exposed by thepeeling of the carrier, a step of subjecting the region containing thethrough-hole and/or the blind via to desmear treatment, a step ofapplying a catalytic nucleus to the region containing the through-holeand/or the blind via, a step of providing an etching resist on thesurface of the ultra-thin copper layer exposed by the peeling of thecarrier, a step of forming a circuit pattern by exposing the etchingresist to light, a step of forming a circuit by removing the ultra-thincopper layer and the catalytic nucleus by a process such as etchingusing an etchant such as an acid or plasma etching, a step of removingthe etching resist, a step of providing a solder resist or platingresist on the surface of the insulating substrate exposed by the removalof the ultra-thin copper layer and the catalytic nucleus by a processsuch as etching using an etchant such as an acid or plasma etching, anda step of providing an electroless plating layer in the region nothaving the solder resist or plating resist.

The subtractive process in the present invention refers to a method offorming a conductor pattern by selectively removing the unnecessaryportion of the copper foil on a copper clad laminate by, for example,etching.

Accordingly, in an embodiment of the method of producing the printedwiring board of the present invention employing the subtractive process,the method includes a step of preparing a copper foil with a carrier ofthe present invention and an insulating substrate, a step of laminatingthe copper foil with a carrier and the insulating substrate, a step ofpeeling the carrier of the copper foil with a carrier from the laminatecomposed of the copper foil with a carrier and the insulating substrate,a step of providing a through-hole and/or a blind via in the ultra-thincopper layer and the insulating substrate exposed by the peeling of thecarrier, a step of subjecting the region containing the through-holeand/or the blind via to desmear treatment, a step of providing anelectroless plating layer in the region containing the through-holeand/or the blind via, a step of providing a electroplating layer on thesurface of the electroless plating layer, a step of providing an etchingresist on the surface of the electroplating layer and/or the ultra-thincopper layer, a step of forming a circuit pattern by exposing theetching resist to light, a step of forming a circuit by removing theultra-thin copper layer, the electroless plating layer, and theelectroplating layer by a process such as etching using an etchant suchas an acid or plasma etching, and a step of removing the etching resist.

In another embodiment of the method of producing the printed wiringboard of the present invention employing the subtractive process, themethod includes a step of preparing a copper foil with a carrier of thepresent invention and an insulating substrate, a step of laminating thecopper foil with a carrier and the insulating substrate, a step ofpeeling the carrier of the copper foil with a carrier from the laminatecomposed of the copper foil with a carrier and the insulating substrate,a step of providing a through-hole and/or a blind via in the ultra-thincopper layer and the insulating substrate exposed by the peeling of thecarrier, a step of subjecting the region containing the through-holeand/or the blind via to desmear treatment, a step of providing anelectroless plating layer in the region containing the through-holeand/or the blind via, a step of forming a mask on the surface of theelectroless plating layer, a step of providing an electroplating layeron the surface of the electroless plating layer not provided with themask, a step of providing an etching resist on the surface of theelectroplating layer and/or the ultra-thin copper layer, a step offorming a circuit pattern by exposing the etching resist to light, astep of forming a circuit by removing the ultra-thin copper layer andthe electroless plating layer by a process such as etching using anetchant such as an acid or plasma etching, and a step of removing theetching resist.

The step of providing a through-hole and/or a blind via and thesubsequent desmear step may be omitted. In the case of the copper foilwith a carrier of the present invention, the peeling position is mainlythe interface between the carrier and the intermediate layer or theinterface between the intermediate layer and the ultra-thin copperlayer. When the intermediate layer is a multilayer, peeling may beperformed at the interfaces of the multiple layers.

EXAMPLES

The present invention will now be described by examples and comparativeexamples. The following examples are preferred one, and the scope of thepresent invention should not be limited to these examples. Accordingly,modification and other examples or embodiments included in the technicalidea of the present invention are all included in the present invention.

For comparison with the present invention, comparative examples are alsoshown.

A long electrolyzed copper foil (JTC, manufactured by JX Nippon Mining &Metals Corporation) having a thickness of 35 μm was used as a carrier.On the glossy surface (shiny surface) of this copper foil, a Ni layerwas formed at a deposition amount of 4000 μg/dm² by electroplating withcontinuous roll-to-roll plating line under the following conditions.

(Ni Layer)

-   -   Nickel sulfate: 200 to 300 g/L    -   Trisodium citrate: 2 to 10 g/L    -   pH: 2 to 4    -   Bath temperature: 40 to 70° C.    -   Current density: 1 to 15 A/dm²

After washing with water and pickling, a Cr layer was subsequentlydeposited on the Ni layer at a deposition amount of 11 μg/dm² byelectrolytic chromate treatment using continuous roll-to-roll platingline under the following conditions.

(Electrolytic Chromate Treatment)

-   -   Liquid composition: potassium dichromate: 1 to 10 g/L, zinc: 0        to 5 g/L    -   pH: 3    -   to 4    -   Liquid temperature: 50 to 60° C.    -   Current density: 0.1 to 2.6 A/dm²    -   Coulomb quantity: 0.5 to 30 As/dm²

Subsequently, an ultra-thin copper layer having a thickness of 2 to 15μm was formed on the Cr layer by electroplating with continuousroll-to-roll plating line under the conditions shown in Examples andComparative Examples below to produce a copper foil with a carrier.

-   -   Ultra-thin copper layer    -   Copper concentration: 30 to 120 g/L    -   H₂SO₄ concentration: 20 to 120 g/L    -   Electrolytic solution temperature: 20 to 80° C.    -   Glue: 1 to 20 ppm    -   Current density: 10 to 100 A/dm²

Example 1

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows. Thetreatment conditions are shown below. These are all steps for formingthe roughened layer in the copper foil of the present invention. Theratio of current density to limiting current density during rougheningparticle formation was adjusted to 2.50.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

After the roughening treatment, normal plating shown below wasperformed. The treatment conditions were as follows.

(Liquid Composition 2)

-   -   Cu: 40 g/L    -   H₂SO₄: 100 g/L

(Electroplating temperature 1): 40° C.

(Electric Current Condition 1)

-   -   Current density: 30 A/dm²    -   Roughening coulomb quantity: 150 As/dm²

Subsequently, a heat-resistant/rustproof layer was subjected toelectrolytic chromate treatment.

Electrolytic Chromate Treatment (Chromium/Zinc Treatment (Acidic Bath))

-   -   CrO₃: 1.5 g/L    -   ZnSO₄.7H₂O: 2.0 g/L    -   Na₂SO₄: 18 g/L    -   pH: 4.6    -   Bath temperature: 37° C.    -   Current density: 2.0 A/dm²    -   Time: 1 to 30 seconds

(The pH was adjusted with sulfuric acid or potassium hydroxide.)

Subsequently, the chromate film layer was subjected to silane treatment(by application).

The silane treatment conditions were as follows.

3-Glycidoxypropyltrimethoxysilane: 0.2%

An FIB-SIM photograph of the roughened layer of Example 1 is shown inthe left of FIG. 2. In this roughened layer, the surface roughness Rzwas 1.17 μm, the average diameter D1 at the particle bottom being apartfrom the bottom of each particle by 10% of the particle length was 0.57μm, the particle length L1 was 2.68 μm, and the ratio L1/D1 of theparticle length L1 to the average diameter D1 at the particle bottom was4.74. FIG. 2 shows that the roughened layer was formed in an acicular orrod-like particle shape. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.57, average diameter D2 atthe particle middle: 0.83, average diameter D3 at the particle end:0.68, ratio D2/D1 of the average diameter at the middle position to thatat the bottom position: 1.47, ratio D3/D1 of the average diameter at theend position to that at the bottom position: 1.21, and ratio D3/D2 ofthe average diameter at the end position to that at the middle position:0.83. These results all satisfied the preferred requirements of thepresent invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT. Thecopper layer laminated to the resin was removed by etching. An SEMphotograph of the surface of the resin (replica) after the removal ofthe copper layer is shown in the right of FIG. 2.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 51% and that the density of the holes was 2.10holes/μm2. Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was satisfied.

The copper foil was laminated to the resin (GHPL-830MBT) as describedabove, and peel strengths of the laminate in a normal state and afterheating were measured. The results are also shown in Table 1. Thecircuit width for the peel strength was 10 mm. The peel strength in anormal state was 1.01 kg/cm, and the peel strength after heating was0.94 kg/cm. Both peel strengths were higher than those in ComparativeExamples described below.

TABLE 1 Ratio of current density to limiting Peel strength Rougheningparticles current density during Normal After Bottom Intermediateroughening particle state heating Roughness width Middle End layerformation (kg/cm) (mm) D1 D2 D3 D2/D1 Comparative Ni/chromate 10.50 0.540.53 1.13 0.12 0.74 0.74 5.93 Example 1 Comparative Ni/chromate 9.500.58 0.49 1.02 0.15 0.65 0.65 4.25 Example 2 Comparative Ni/chromate9.80 0.73 0.69 0.88 0.14 0.65 0.65 4.50 Example 3 Example 1 Ni/chromate2.50 1.01 0.94 1.17 0.57 0.83 0.68 1.47 Example 2 Ni/chromate 3.10 0.810.78 1.51 0.51 0.78 0.68 1.51 Example 3 Ni/chromate 4.30 0.84 0.77 1.560.59 0.73 0.65 1.23 Example 4 Ni/chromate 3.50 0.90 0.86 1.62 0.89 1.050.98 1.18 Example 5 Ni/chromate 4.80 0.91 0.84 1.01 0.26 0.84 0.79 3.23Example 6 Ni/chromate 3.20 0.91 0.91 1.48 0.60 0.84 0.78 1.39 Rougheningparticles Replica Ratio Density Area ratio D3/D1 D3/D2 Length(length/width) (particles/μm²) (%) Comparative 5.93 1.00 3.87 30.97 1.06 2% Example 1 Comparative 4.25 1.00 2.83 18.54 2.11  4% Example 2Comparative 4.50 1.00 2.98 20.64 3.12 14% Example 3 Example 1 1.21 0.832.68 4.74 2.10 51% Example 2 1.32 0.87 2.68 5.21 1.93 29% Preferredvalue Example 3 1.10 0.89 2.68 4.52 1.77 43% | Example 4 1.10 0.93 2.983.33 2.02 78% | Example 5 3.06 0.95 2.68 10.34 2.65 40% | Example 6 1.300.94 2.68 4.44 2.22 93% ↓ Resin: MBT-830 Peel strength measurementcircuit width: 10 mm Roughening particle bottom width measurementprocess: JIS H 0501 Section 7 Cutting method

Example 2

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. These are all steps for forming theroughened layer of the copper foil of the present invention. The ratioof current density to limiting current density during rougheningparticle formation was adjusted to 3.10.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In this roughened layer, the surface roughness Rz was 1.51 μm, theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length was 0.51 μm, the particlelength L1 was 2.68 μm, and the ratio L1/D1 of the particle length L1 tothe average diameter D1 at the particle bottom was 5.21. It was presumedfrom FIG. 2 that the roughened layer was formed in an acicular orrod-like particle shape. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.51 μm, average diameter D2at the particle middle: 0.78 μm, average diameter D3 at the particleend: 0.68 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 1.51, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 1.32, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 0.87. These results all satisfied the preferredrequirements of the present invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT(product name, manufactured by Mitsubishi Gas Chemical Company, Inc.),and the copper layer was removed by etching. It was observed that thesum of areas of holes accounting for the resin surface having theunevenness transferred from the roughened surface of the copper foil was29% and that the density of the holes was 1.93 holes/μm². Thus, therequirement of the present invention that the sum of areas of holesaccounts for 20% or more was satisfied.

The copper foil was laminated to the resin as described above, and peelstrengths of the laminate in a normal state and after heating weremeasured. The results are also shown in Table 1. The circuit width forthe peel strength was 10 mm. The peel strength in a normal state was0.81 kg/cm, and the peel strength after heating was 0.78 kg/cm. Bothpeel strengths were higher than those in Comparative Examples describedbelow.

Example 3

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. These are all steps for forming theroughened layer of the copper foil of the present invention. The ratioof current density to limiting current density during rougheningparticle formation was adjusted to 4.30.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In this roughened layer, the surface roughness Rz was 1.56 μm, theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length was 0.59 μm, the particlelength L1 was 2.68 μm, and the ratio L1/D1 of the particle length L1 tothe average diameter D1 at the particle bottom was 4.52. It was presumedfrom FIG. 2 that the roughened layer was formed in an acicular orrod-like particle shape. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.51 μm, average diameter D2at the particle middle: 0.73 μm, average diameter D3 at the particleend: 0.65 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 1.23, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 1.10, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 0.89. These results all satisfied the preferredrequirements of the present invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin MBT-830, and thecopper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 43% and that the density of the holes was 1.77holes/μm². Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was satisfied.

The copper foil was laminated to the resin as described above, and peelstrengths of the laminate in a normal state and after heating weremeasured. The results are also shown in Table 1. The circuit width forthe peel strength was 10 mm. The peel strength in a normal state was0.84 kg/cm, and the peel strength after heating was 0.77 kg/cm. Bothpeel strengths were higher than those in Comparative Examples describedbelow.

Example 4

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 3 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. These are all steps for forming theroughened layer of the copper foil of the present invention. The ratioof current density to limiting current density during rougheningparticle formation was adjusted to 3.50.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In this roughened layer, the surface roughness Rz was 1.62 μm, theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length was 0.89 μm, the particlelength L1 was 2.98 μm, and the ratio L1/D1 of the particle length L1 tothe average diameter D1 at the particle bottom was 3.33. It was presumedfrom FIG. 2 that the roughened layer was formed in an acicular orrod-like particle shape. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.89 μm, average diameter D2at the particle middle: 1.65 μm, average diameter D3 at the particleend: 0.98 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 1.18, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 1.10, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 0.93. These results all satisfied the preferredrequirements of the present invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT, andthe copper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 78% and that the density of the holes was 2.02holes/μm². Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was satisfied.

The copper foil was laminated to the resin as described above, and peelstrengths of the laminate in a normal state and after heating weremeasured. The results are also shown in Table 1. The circuit width forthe peel strength was 10 mm. The peel strength in a normal state was0.90 kg/cm, and the peel strength after heating was 0.86 kg/cm. Bothpeel strengths were higher than those in Comparative Examples describedbelow.

Example 5

The rough surface (mat surface: M surface) of the copper foil with acarrier (thickness of ultra-thin copper layer: 2 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. These are all steps for forming theroughened layer of the copper foil of the present invention. The ratioof current density to limiting current density during rougheningparticle formation was adjusted to 4.80.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In this roughened layer, the surface roughness Rz was 1.01 μm, theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length was 0.26 μm, the particlelength L1 was 2.68 μm, and the ratio L1/D1 of the particle length L1 tothe average diameter D1 at the particle bottom was 10.34. It waspresumed from FIG. 2 that the roughened layer was formed in an acicularor rod-like particle shape. The diameters of the roughening particleswere measured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.26 μm, average diameter D2at the particle middle: 0.84 μm, average diameter D3 at the particleend: 0.79 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 3.23, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 3.06, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 0.95. These results all satisfied the preferredrequirements of the present invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT andthe copper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 40% and that the density of the holes was 2.65holes/μm². Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was satisfied.

The copper foil was laminated to the resin as described above, and peelstrengths of the laminate in a normal state and after heating weremeasured. The results are also shown in Table 1. The circuit width forthe peel strength was 10 mm. The peel strength in a normal state was0.91 kg/cm, and the peel strength after heating was 0.84 kg/cm. Bothpeel strengths were higher than those in Comparative Examples describedbelow.

Example 6

The rough surface (mat surface: M surface) of the copper foil with acarrier (thickness of ultra-thin copper layer: 12 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. These are all steps for forming theroughened layer of the copper foil of the present invention. The ratioof current density to limiting current density during rougheningparticle formation was adjusted to 3.20.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In this roughened layer, the surface roughness Rz was 1.48 μm, theaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length was 0.60 μm, the particlelength L1 was 2.68 μm, and the ratio L1/D1 of the particle length L1 tothe average diameter D1 at the particle bottom was 4.44. It was presumedfrom FIG. 2 that the roughened layer was formed in an acicular orrod-like particle shape. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

The roughened layer of the copper foil satisfied the requirements of thepresent invention that the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength is 0.2 to 1.0 μm and that the ratio L1/D1 of the particle lengthL1 to the average diameter D1 at the particle bottom is 15 or less.These requirements are indispensable for achieving the presentinvention. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.60 μm, average diameter D2at the particle middle: 0.84 μm, average diameter D3 at the particleend: 0.78 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 1.39, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 1.30, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 0.94. These results all satisfied the preferredrequirements of the present invention.

It should be readily understood that these are not fundamentalrequirements, i.e., not indispensable requirements of the presentinvention and that these are preferred requirements.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT, andthe copper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 93% and that the density of the holes was 2.22holes/μm2. Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was satisfied.

The copper foil was laminated to the resin as described above, and peelstrengths of the laminate in a normal state and after heating weremeasured. The results are also shown in Table 1. The circuit width forthe peel strength was 10 mm. The peel strength in a normal state was0.91 kg/cm, and the peel strength after heating was 0.91 kg/cm. Bothpeel strengths were higher than those in Comparative Examples describedbelow.

Comparative Example 1

The rough surface (mat surface: M surface) of copper foil with a carrier(thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. The ratio of current density tolimiting current density during roughening particle formation wasadjusted to 10.50.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

An SEM photograph of the roughened layer of Comparative Example 1 isshown in the left of FIG. 3. In this roughened layer, the surfaceroughness Rz was 1.13 μm, the average diameter D1 at the particle bottombeing apart from the bottom of each particle by 10% of the particlelength was 0.12 μm giving a small bottom width, the particle length L1was 3.87 μm, and the ratio L1/D1 of the particle length L1 to theaverage diameter D1 at the particle bottom was 30.97. It was presumedfrom FIG. 3 that the roughened layer was formed in an acicular ordendrite-like particle shape that did not satisfy the requirements ofthe present invention. The diameters of the roughening particles weremeasured in accordance with JIS H 0501, Section 7, Cutting method.

As described above, the roughened layer of the copper foil did notsatisfy the requirements of the present invention that the averagediameter D1 at the particle bottom being apart from the bottom of eachparticle by 10% of the particle length is 0.2 to 1.0 μm and that theratio L1/D1 of the particle length L1 to the average diameter D1 at theparticle bottom is 15 or less. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.12 μm, average diameter D2at the particle middle: 0.74 μm, average diameter D3 at the particleend: 0.74 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 5.93, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 5.93, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 1.00. These results all did not satisfy the preferredrequirements of the present invention.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT. Thecopper layer was removed by etching. An SEM photograph of the surface ofthe resin (replica) after the removal of the copper layer by etching isshown in the right of FIG. 3. It was observed that the sum of areas ofholes accounting for the resin surface having the unevenness transferredfrom the roughened surface of the copper foil was 2% and that thedensity of the holes was 1.06 holes/μm2. Thus, the requirement of thepresent invention that the sum of areas of holes accounts for 20% ormore was not satisfied.

The copper foil was laminated to the resin GHPL-830MBT as describedabove, and peel strengths of the laminate in a normal state and afterheating were measured. The results are also shown in Table 1. Thecircuit width for the peel strength was 10 mm. The peel strength in anormal state was 0.54 kg/cm, and the peel strength after heating was0.53 kg/cm. Both peel strengths were considerably low compared to thosein Examples described above. In the copper foil including rougheningparticles having a thin bottom portion as described above, animprovement in peel strength could not be expected because of theoccurrence of peeling at the interface between the copper layer and theroughening particles when separating the copper foil and the resin.

Comparative Example 2

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. The ratio of current density tolimiting current density during roughening particle formation wasadjusted to 9.50.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   Sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In the roughened layer of Comparative Example 2, the surface roughnessRz was 1.02 μm, the average diameter D1 at the particle bottom beingapart from the bottom of each particle by 10% of the particle length was0.15 μm giving a small bottom width, the particle length L1 was 2.83 μm,and the ratio L1/D1 of the particle length L1 to the average diameter D1at the particle bottom was 18.54. It was presumed from FIG. 3 that theroughened layer was formed in an acicular or dendrite-like particleshape that did not satisfy the requirements of the present invention.The diameters of the roughening particles were measured in accordancewith JIS H 0501, Section 7, Cutting method.

As described above, the roughened layer of the copper foil did notsatisfy the requirements of the present invention that the averagediameter D1 at the particle bottom being apart from the bottom of eachparticle by 10% of the particle length is 0.2 to 1.0 μm and that theratio L1/D1 of the particle length L1 to the average diameter D1 at theparticle bottom is 15 or less. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.15 μm, average diameter D2at the particle middle: 0.65 μm, average diameter D3 at the particleend: 0.65 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 4.25, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 4.25, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 1.00. These results all did not satisfy the preferredrequirements of the present invention.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT. Thecopper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 4% and that the density of the holes was 2.11holes/μm2. Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was not satisfied.

The copper foil was laminated to the resin GHPL-830MBT as describedabove, and peel strengths of the laminate in a normal state and afterheating were measured. The results are also shown in Table 1. Thecircuit width for the peel strength was 10 mm. The peel strength in anormal state was 0.54 kg/cm, and the peel strength after heating was0.53 kg/cm. Both peel strengths were considerably low compared to thosein Examples described above.

In the copper foil including roughening particles having a thin bottomportion as described above, an improvement in peel strength could not beexpected because of the occurrence of peeling at the interface betweenthe copper layer and the roughening particles when separating the copperfoil and the resin.

Comparative Example 3

The rough surface (mat surface: M surface) of a copper foil with acarrier (thickness of ultra-thin copper layer: 5 μm, roughness Rz ofroughness-forming surface of ultra-thin copper layer: 0.6 μm) treated asdescribed above was subjected to roughening plating as follows and tonormal plating as in Example 1. The treatment conditions for theroughening plating are shown below. The ratio of current density tolimiting current density during roughening particle formation wasadjusted to 9.80.

(Liquid Composition 1)

-   -   Cu: 15 g/L    -   H₂SO₄: 100 g/L    -   W: 3 mg/L    -   sodium dodecyl sulfate amount: 10 ppm

(Electroplating temperature 1): 50° C.

In the roughened layer of Comparative Example 3, the surface roughnessRz was 0.88 μm, the average diameter D1 at the particle bottom beingapart from the bottom of each particle by 10% of the particle length was0.14 μm giving a small bottom width, the particle length L1 was 2.98 μm,and the ratio L1/D1 of the particle length L1 to the average diameter D1at the particle bottom was 20.64. It was presumed from FIG. 3 that theroughened layer was formed in an acicular or dendrite-like particleshape that did not satisfy the requirements of the present invention.The diameters of the roughening particles were measured in accordancewith JIS H 0501, Section 7, Cutting method.

As described above, the roughened layer of the copper foil did notsatisfy the requirements of the present invention that the averagediameter D1 at the particle bottom being apart from the bottom of eachparticle by 10% of the particle length is 0.2 to 1.0 μm and that theratio L1/D1 of the particle length L1 to the average diameter D1 at theparticle bottom is 15 or less. The results are shown in Table 1.

Table 1 also shows other data of the roughening particles, i.e., averagediameter (width) D1 at the particle bottom: 0.14 μm, average diameter D2at the particle middle: 0.65 μm, average diameter D3 at the particleend: 0.65 μm, ratio D2/D1 of the average diameter at the middle positionto that at the bottom position: 4.50, ratio D3/D1 of the averagediameter at the end position to that at the bottom position: 4.50, andratio D3/D2 of the average diameter at the end position to that at themiddle position: 1.00. These results all did not satisfy the preferredrequirements of the present invention.

Subsequently, the copper foil was laminated to a resin GHPL-830MBT. Thecopper layer was removed by etching.

It was observed that the sum of areas of holes accounting for the resinsurface having the unevenness transferred from the roughened surface ofthe copper foil was 14% and that the density of the holes was 3.12holes/μm2. Thus, the requirement of the present invention that the sumof areas of holes accounts for 20% or more was not satisfied.

The copper foil was laminated to the resin GHPL-830MBT as describedabove, and peel strengths of the laminate in a normal state and afterheating were measured. The results are also shown in Table 1. Thecircuit width for the peel strength was 10 mm. The peel strength in anormal state was 0.54 kg/cm, and the peel strength after heating was0.53 kg/cm. Both peel strengths were considerably low compared to thosein Examples described above. In the copper foil including rougheningparticles having a thin bottom portion as described above, animprovement in peel strength could not be expected because of theoccurrence of peeling at the interface between the copper layer and theroughening particles when separating the copper foil and the resin.

As described above, the copper foil for printed wiring boards of thepresent invention includes acicular fine roughening particles on atleast one surface of the copper foil instead of the roundish orspherical projections or dendrite-like crystal grains that have beenconventionally believed to be good for roughening treatment. As aresult, the adhesion strength between the copper foil itself and a resinis increased, and it is thereby possible to provide high peel strengthto a substrate for package in chemical treatment during fine-patternformation. It is understood that the present invention has a notableeffect of providing a copper foil that allows fine etching and a methodof producing the copper foil.

Example 21

A copper layer was formed under the same conditions as those in Example1 except that a CoMo alloy intermediate layer was formed between thecarrier and the copper foil. In this case, the CoMo alloy intermediatelayer was produced by plating in a plating solution having the followingliquid composition.

(Liquid Composition)

-   -   CoSO₄.7H₂O: 0.5 to 100 g/L    -   Na₂MoO₄.2H₂O: 0.5 to 100 g/L    -   Sodium citrate dihydrate: 20 to 300 g/L

(Temperature): 10 to 70° C.

(pH): 3 to 5

(Current density): 0.1 to 60 A/dm²

The copper foil was laminated to the resin (GHPL-830MBT) as describedabove, and peel strengths of the laminate in a normal state and afterheating were measured. The results are shown in Table 2. The circuitwidth for the peel strength was 10 mm.

The peel strength in a normal state was 1.01 kg/cm, and the peelstrength after heating was 0.94 kg/cm. Both peel strengths were higherthan those in Comparative Examples as described.

TABLE 2 Ratio of current density to limiting Peel strength Rougheningparticles current density during Normal After Bottom Intermediateroughening particle state heating Roughness width Middle End layerformation (kg/cm) (μm) D1 D2 D3 Example 21 CoMo alloy 2.50 1.01 0.941.17 0.57 0.83 0.68 Example 22 Cr 3.10 0.81 0.78 1.51 0.51 0.78 0.68Example 23 Cr/CuP 4.30 0.84 0.77 1.56 0.59 0.73 0.65 Example 24 Ni/Cr3.50 0.90 0.86 1.62 0.89 1.05 0.98 Example 25 Co/chromate 4.80 0.91 0.841.01 0.26 0.84 0.79 Example 26 Organic compound 3.20 0.91 0.91 1.48 0.600.84 0.78 Roughening particles Replica Ratio Density Area ratio D2/D1D3/D1 D3/D2 Length (length/width) (particles/μm²) (%) Example 21 1.471.21 0.83 2.68 4.74 2.10 51% Example 22 1.51 1.32 0.87 2.68 5.21 1.9329% Example 23 1.23 1.10 0.89 2.68 4.52 1.77 43% Example 24 1.18 1.100.93 2.98 3.33 2.02 78% Example 25 3.23 3.06 0.95 2.68 10.34 2.65 40%Example 26 1.39 1.30 0.94 2.68 4.44 2.22 93% Resin: MBT-830 Peelstrength measurement circuit width: 10 mm Roughening particle bottomwidth measurement process: JIS H 0501 Section 7 Cutting method

Example 22

A copper layer was formed under the same conditions as those in Example2 except that a Cr intermediate layer was formed between the carrier andthe copper foil. In this case, the Cr intermediate layer was produced byplating in a plating solution having the following liquid composition.

(Liquid Composition)

-   -   CrO₃: 200 to 400 g/L    -   H₂SO₄: 1.5 to 4 g/L

(pH): 1 to 4

(Liquid temperature): 45 to 60° C.

(Current density): 10 to 40 A/dm²

The copper foil was laminated to the resin (MBT-830) as described above,and peel strengths of the laminate in a normal state and after heatingwere measured. The results are shown in Table 2.

The circuit width for the peel strength was 10 mm. The peel strength ina normal state was 0.81 kg/cm, and the peel strength after heating was0.78 kg/cm. Both peel strengths were higher than those in ComparativeExamples as described.

Example 23

A copper layer was formed under the same conditions as those in Example3 except that a Cr/CuP intermediate layer was formed between the carrierand the copper foil. In this case, the Cr/CuP intermediate layer wasproduced by plating in a plating solution having the following liquidcomposition.

(Liquid Composition 1)

-   -   CrO₃: 200 to 400 g/L    -   H₂SO₄: 1.5 to 4 g/L

(pH): 1 to 4

(Liquid temperature): 45 to 60° C.

(Current density): 10 to 40 A/dm²

(Liquid Composition 2)

-   -   Cu₂P₂O₇.3H₂O: 5 to 50 g/L    -   K₄P₂O₇: 50 to 300 g/L

(Temperature): 30 to 60° C.

(pH): 8 to 10

(Current density): 0.1 to 1.0 A/dm²

The copper foil was laminated to the resin (MBT-830) as described above,and peel strengths of the laminate in a normal state and after heatingwere measured. The results are shown in Table 2.

The circuit width for the peel strength was 10 mm. The peel strength ina normal state was 0.84 kg/cm, and the peel strength after heating was0.77 kg/cm. Both peel strengths were higher than those in ComparativeExamples as described.

Example 24

A copper layer was formed under the same conditions as those in Example4 except that a Ni/Cr intermediate layer was formed between the carrierand the copper foil. In this case, the Ni/Cr intermediate layer wasproduced by plating in a plating solution having the following liquidcomposition.

(Liquid Composition 1)

-   -   NiSO₄.6H₂O: 250 to 300 g/L    -   NiCl₂.6H₂O: 35 to 45 g/L    -   Boric acid: 10 to 50 g/L

(pH): 2 to 6

(Bath temperature): 30 to 70° C.

(Current density): 0.1 to 50 A/dm²

(Liquid Composition 2)

-   -   CrO₃: 200 to 400 g/L    -   H₂SO₄: 1.5 to 4 g/L

(pH): 1 to 4

(Liquid temperature): 45 to 60° C.

(Current density): 10 to 40 A/dm²

The copper foil was laminated to the resin (MBT-830) as described above,and peel strengths of the laminate in a normal state and after heatingwere measured. The results are shown in Table 2.

The circuit width for the peel strength was 10 mm. The peel strength ina normal state was 0.90 kg/cm, and the peel strength after heating was0.86 kg/cm. Both peel strengths were higher than those in ComparativeExamples as described.

Example 25

A copper layer was formed under the same conditions as those in Example4 except that a Co/chromate treated intermediate layer was formedbetween the carrier and the copper foil.

In this case, the Co/chromate treated intermediate layer was produced byplating in a plating solution having the following liquid composition.

(Liquid Composition 1)

-   -   CoSO₄.7H₂O: 10 to 100 g/L    -   Sodium citrate dihydrate: 30 to 200 g/L

(Temperature): 10 to 70° C.

(pH): 3 to 5

(Current density): 0.1 to 60 A/dm²

(Liquid Composition 2)

-   -   CrO₃: 1 to 10 g/L

(Temperature): 10 to 70° C.

(pH): 10 to 12

(Current density): 0.1 to 1.0 A/dm²

The copper foil was laminated to the resin (MBT-830) as described above,and peel strengths of the laminate in a normal state and after heatingwere measured. The results are shown in Table 2.

The circuit width for the peel strength was 10 mm. The peel strength ina normal state was 0.91 kg/cm, and the peel strength after heating was0.84 kg/cm. Both peel strengths were higher than those in ComparativeExamples as described.

Example 26

A copper layer was formed under the same conditions as those in Example4 except that an organic compound intermediate layer was formed betweenthe carrier and the copper foil.

In this case, the organic compound intermediate layer was produced byspraying an aqueous 1 to 10 g/L carboxybenzotriazole solution at aliquid temperature of 40° C. and a pH of 5 for 10 to 60 seconds.

The copper foil was laminated to the resin (MBT-830) as described above,and peel strengths of the laminate in a normal state and after heatingwere measured. The results are shown in Table 2.

The circuit width for the peel strength was 10 mm. The peel strength ina normal state was 0.91 kg/cm, and the peel strength after heating was0.91 kg/cm. Both peel strengths were higher than those in ComparativeExamples as described.

INDUSTRIAL APPLICABILITY

As described above, the present invention has a notable effect ofproviding a copper foil with a carrier including acicular fineroughening particles on at least one surface of the copper foil with acarrier and thereby enhancing the adhesion strength of the copper foilitself with resin so as to provide high peel strength to a substrate forpackage also in chemical treatment during fine-pattern formation and toallow fine etching and providing a method of producing the copper foilwith corrier.

In recent increases in fineness of printed circuit patterns and infrequency, the copper foil with a carrier for a printed circuit board ofthe present invention is significantly effective as a copper foil forprinted circuits (copper foil for a semiconductor package substrate) ora substrate for semiconductor package composed of a copper foil for asemiconductor package substrate and a resin for semiconductor packagebonded to each other.

1-27. (canceled)
 28. A copper foil with a carrier comprising a carrier,an intermediate layer, and an ultra-thin copper layer laminated in thisorder, wherein the ultra-thin copper layer includes a roughened layer ona surface thereof, and the roughened layer comprises particles having anaverage diameter D1 at the particle bottom being apart from the bottomof each particle by 10% of the particle length L1 of 0.2 to 1.0 μm andhaving a ratio L1/D1 of the particle length L1 to the average diameterD1 at the particle bottom of 15 or less.
 29. The copper foil with acarrier according to claim 28, wherein the roughened layer on a surfaceof the ultra-thin copper layer has a ratio D2/D1 of the average diameterD2 at the particle middle being apart from the bottom of each particleby 50% of the particle length to the average diameter D1 at the particlebottom of 1 to
 4. 30. The copper foil with a carrier according to claim29, wherein the average diameter D2 at the particle middle is 0.7 μm to1.5 μm.
 31. The copper foil with a carrier according to claim 29,wherein the ratio D2/D3 of the average diameter D2 at the particlemiddle to the average diameter D3 at the particle end being apart fromthe bottom of each particle by 90% of the particle length is 0.8 to 1.0.32. The copper foil with a carrier according to claim 31, wherein theaverage diameter D3 at the particle end is 0.7 μm to 1.5 μm.
 33. Thecopper foil with a carrier according to claim 28, comprising a resinlayer on the roughened layer.
 34. The copper foil with a carrieraccording to claim 28, further comprising at least one layer selectedfrom the group consisting of heat-resistant/rustproof layers eachcontaining at least one element selected from the group consisting ofzinc, nickel, copper, phosphorus, and cobalt, chromate film layers, andsilane coupling agent layers, on the roughened layer.
 35. The copperfoil with a carrier according to claim 28, further comprising aheat-resistant/rustproof layer containing at least one element selectedfrom the group consisting of zinc, nickel, copper, phosphorus, andcobalt on the roughened layer and a chromate film layer on theheat-resistant/rustproof layer.
 36. The copper foil with a carrieraccording to claim 28, further comprising a heat-resistant/rustprooflayer containing at least one element selected from the group consistingof zinc, nickel, copper, phosphorus, and cobalt on the roughened layer,a chromate film layer on the heat-resistant/rustproof layer, and asilane coupling agent layer on the chromate film layer.
 37. The copperfoil with a carrier according to claim 34, comprising a resin layer onat least one layer selected from the group consisting of theheat-resistant/rustproof layer, the chromate film layer, and the silanecoupling agent layer.
 38. The copper foil with a carrier according toclaim 33, wherein the resin layer is a resin for adhesion.
 39. Thecopper foil with a carrier according to claim 33, wherein the resinlayer comprises a resin in a semi-cured state.
 40. A copper foil with acarrier comprising a carrier, an intermediate layer, and an ultra-thincopper layer laminated in this order, wherein the copper foil with acarrier comprises a roughened layer on a surface of the ultra-thincopper layer; and when a resin layer is laminated to the roughened layerof the copper foil with a carrier, then the carrier and the intermediatelayer are peeled from the ultra-thin copper layer, and then theultra-thin copper layer is removed by etching, the sum of areas of holeson a roughened surface of the resin layer having unevenness transferredfrom a surface of the roughened layer accounts for 20% or more of theroughened surface of the resin layer.
 41. The copper foil with a carrieraccording to claim 28, wherein when a resin layer is laminated to theroughened layer of the copper foil, then the carrier and theintermediate layer are peeled from the ultra-thin copper layer, and thenthe ultra-thin copper layer is removed by etching, the sum of areas ofholes on a roughened surface of the resin layer having unevennesstransferred from a surface of the roughened layer accounts for 20% ormore of the roughened surface of the resin layer.
 42. The copper foilwith a carrier according to claim 28, wherein the intermediate layer isat least one layer containing at least one selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, alloys,hydrates, and oxides thereof, and organic compounds.
 43. The copper foilwith a carrier according to claim 28, wherein the intermediate layercomprises, from the carrier side, a monometal layer of one elementselected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu,and Al or an alloy layer of one or more elements selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al; and a layer of ahydrate or oxide of one or more elements selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al.
 44. The copperfoil with a carrier according to claim 28, wherein the intermediatelayer comprises Ni and Cr, a deposition amount of Cr of the intermediatelayer is 10 μg/dm² to 100 μg/dm², and a deposition amount of Ni is 1000μg/dm² to 40000 μg/dm².
 45. A method of producing a copper foil with acarrier comprising a carrier, an intermediate layer, and an ultra-thincopper layer laminated in this order, the copper foil with a carriercomprising a roughened layer on a surface of the ultra-thin copperlayer, wherein the method comprises the step of forming the roughenedlayer by using a sulfuric acid/copper sulfate electrolytic bathcontaining at least one material selected from alkyl sulfates, tungsten,and arsenic.
 46. A method of producing a copper foil with a carrieraccording to claim 28, comprising the step of forming the roughenedlayer by using a sulfuric acid/copper sulfate electrolytic bathcontaining at least one material selected from the group consisting ofalkyl sulfates, tungsten, and arsenic.
 47. The method according to claim45, comprising the step of forming a heat-resistant/rustproof layercontaining at least one element selected from the group consisting ofzinc, nickel, copper, phosphorus, and cobalt on the roughened layer,forming a chromate film layer on the heat-resistant/rustproof layer, andforming a silane coupling agent layer on the chromate film layer.
 48. Aprinted wiring board formed by laminating a resin layer to a copper foilwith a carrier including a carrier, an intermediate layer, and anultra-thin copper layer laminated in this order and including aroughened layer on a surface of the ultra-thin copper layer, peeling thecarrier and the intermediate layer from the ultra-thin copper layer,removing the ultra-thin copper layer by etching, forming a circuit onthe exposed resin surface.
 49. A method of producing a printed wiringboard, comprising the step of laminating a resin layer to a copper foilwith a carrier including a carrier, an intermediate layer, and anultra-thin copper layer laminated in this order and including aroughened layer on a surface of the ultra-thin copper layer, peeling thecarrier and the intermediate layer from the ultra-thin copper layer,removing the ultra-thin copper layer by etching, forming a circuit onthe exposed resin surface.
 50. A printed wiring board formed bylaminating a resin layer to a copper foil with a carrier according toclaim 28, peeling the carrier and the intermediate layer from theultra-thin copper layer, removing the ultra-thin copper layer byetching, plating the exposed resin surface by electroless copper platingand electroplating in this order to form a copper layer, and forming acircuit by etching.
 51. A printed wiring board formed by laminating aresin layer to the copper foil with a carrier according to claim 28,peeling the carrier and the intermediate layer from the ultra-thincopper layer, removing the ultra-thin copper layer by etching, andforming a circuit on the exposed resin surface.
 52. A printed wiringboard formed by laminating a resin layer to the copper foil with acarrier according to claim 28, peeling the carrier and the intermediatelayer from the ultra-thin copper layer, removing the ultra-thin copperlayer by etching, forming a copper layer on the exposed resin surface,and forming a circuit.
 53. A printed wiring board produced using thecopper foil with a carrier according to claim
 28. 54. A printed circuitboard produced using the copper foil with a carrier according to claim28.
 55. A copper clad laminate produced using the copper foil with acarrier according to claim
 28. 56. The printed wiring board according toclaim 48, wherein five or more acicular particles are present within acircuit width of 10 μm.
 57. The printed circuit board according to claim54, wherein five or more acicular particles are present within a circuitwidth of 10 μm.
 58. A method of producing a printed wiring board,comprising the steps of preparing the copper foil with a carrieraccording to claim 28 and an insulating substrate, laminating the copperfoil with a carrier and the insulating substrate, peeling the carrier ofthe copper foil with a carrier from the laminate comprising the copperfoil with a carrier and the insulating substrate to form a copper cladlaminate, and forming a circuit by any process selected from the groupconsisting of a semi-additive process, a subtractive process, apartially additive process, and a modified semi-additive process.
 59. Aresin for printed wiring board, having unevenness on a surface thereof,wherein: the unevenness is formed by laminating the resin to a roughenedlayer of a copper foil with a carrier which comprises a carrier, anintermediate layer and an ultra-thin copper layer laminated in thisorder and comprises the roughened layer on a surface of the ultra-thincopper layer; peeling the carrier and the intermediate layer from theultra-thin copper layer; and then removing the ultra-thin copper layerby means of etching, so that the surface of the resin laminated on theroughened layer has unevenness transferred from a surface of theroughened layer, the sum of areas of holes on a roughened surface of theresin layer having unevenness transferred from a surface of theroughened layer accounts for 20% or more of the roughened surface of theresin layer, and the roughened surface of the resin layer is a roughenedsurface for forming a printed wiring board by forming a circuit on theroughened surface.
 60. The resin for printed wiring board according toclaim 59, wherein the resin is a BT (bismaleimide triazine) resin. 61.The resin for printed wiring board according to claim 59, wherein theresin is a BT (bismaleimide triazine) resin-impregnated base material.62. A printed wiring board produced using the resin according to claim59.
 63. A semiconductor package substrate produced using the resinaccording to claim
 59. 64. A printed wiring board produced by platingthe roughened surface of the resin according to claim 59 by electrolesscopper plating and electroplating in this order to form a copper layer,and forming a circuit by etching.
 65. A printed wiring board produced byforming a circuit on the roughened surface of the resin according toclaim 59 by etching.
 66. A printed wiring board produced by forming acopper layer on the roughened surface of the resin according to claim59, and forming a circuit.
 67. A method of producing a printed wiringboard, comprising the steps of plating the roughened surface of theresin according to claim 59 by electroless copper plating andelectroplating in this order to form a copper layer, and forming acircuit by etching.
 68. A method of producing a printed wiring board,comprising the steps of forming a circuit on the roughened surface ofthe resin according to claim 59 by etching.
 69. A method of producing aprinted wiring board, comprising the steps of forming a copper layer onthe roughened surface of the resin according to claim 59, and forming acircuit.